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Christmas is almost here! Are you ready yet? Are you fed up with people asking if you’re ready yet? Have you worked out what to buy for Great-uncle Nigel, who says he neither needs nor wants anything? Always a tricky scenario, that. Consumables are often a safe fallback position. They don’t clutter up the house, and who doesn’t enjoy a nice box of luxury biscuits, or chocolates, or a bottle of champagne, or spirts, or a case of blk water.

Wait, what?

Yes, this mysterious product turned up in my feed a few weeks ago. It’s water (well, so they say), but it’s black. Actually black. Not just black because the bottle’s black, black because the liquid inside it is… black.

It’s black water.

A bit like… cola. Only blacker, and not fizzy, or sweet, or with any discernable flavour other than water.

It raises many questions, doesn’t it? Let’s start with why. Obviously it’s a great marketing gimmick. It definitely looks different. It also comes with a number of interesting claims. The suppliers claim it contains “no nasties” and “only 2 ingredients”, namely spring water and “Fulvic Minerals” (sic). (Hang on, I hear you say, if it’s minerals, plural, surely that’s already more than two ingredients? Oh, but that’s only the start. Stay with me.)

It claims to “balance pH levels” and help “to regulate our highly acidic diets”. Yes, well, I think I’ve covered that before. Absolutely nothing you drink, or eat, does anything to the pH in any part of your body except, possibly, your urine – where you might see a small difference under some circumstances (but even if you do it doesn’t tell you anything significant about the impact of your diet on your long-term health). And bear in mind that a few minutes after you drink any kind of alkaline water it mixes with stomach acid which has a pH of around 2. Honestly, none of that alkaline “goodness” makes it past your pyloric sphincter.

Finally, blk water apparently “replenishes electrolytes”. Hm. Electrolytes are important in the body. They’re ionic species, which means they can conduct electricity. Your muscles and neurons rely on electrical activity, so they are quite important. Like, life or death important. But because of that our bodies are quite good at regulating them, most of the time. If you run marathons in deserts, or get struck down with a nasty case of food poisoning, or have some kind of serious health condition (you’d know about it) you might need to think about electrolytes, but otherwise most of us get what we need from the food and drink we consume normally every day.

Besides which, didn’t they say “only 2 ingredients”? The most common electrolytes in the body are sodium, potassium, magnesium, chloride, hydrogen phosphate and hydrogen carbonate. Most spring waters do contain some, if not all, of these, in greater or smaller amounts, but it’s not going to be enough to effectively “replenish” any of them. If, say, you are running marathons in the desert, the advice is actually to keep a careful eye on your water intake because drinking too much water can dangerously lower your sodium levels. Yes, there are sports drinks that are specifically designed to help with this, but they taste of salt and sugar and/or flavourings which have been added in a desperate attempt to cover up the salty taste. This is apparently not the case with blk water which, to repeat myself, contains “only 2 ingredients”.

Speaking of ingredients, what about those so-called fulvic minerals? Maybe they’re the source of those all-important electrolytes (but not sodium)? And maybe they’re magically tasteless, too?

And perhaps, like other magical objects and substances, they don’t actually exist – as geologist @geolizzy told me on Twitter when I asked.

It’s not looking good for blk water (£47.99 for a case of 24 bottles) at this point. But hang on. Perhaps when they said fulvic minerals, what they meant was fulvic acid – which is a thing, or possibly several things – in a the presence of oh, say, some bicarbonate (*cough* 2 ingredients *cough*).

That could push the pH up to the stated 8-9, and didn’t we learn in school that:
acid + alkali –> salt + water
and maybe, if we’re being generous, we could call the salts of fulvic acids minerals? It’s a bit shaky but… all right.

So what are fulvic acids?

That’s an interesting question. I had never heard of fulvic acids. They do, as it turns out, have a Wikipedia page (Wikipedia is usually very reliable for chemical information, since no one has yet been very interested in spoofing chemical pages to claim things like hydrochloric acid is extracted from the urine of pregnant unicorns) but the information wasn’t particularly enlightening. The page did inform me that fulvic acids are “components of the humus” (in soil) and are “similar to humic acids, with differences being the carbon and oxygen contents, acidity, degree of polymerization, molecular weight, and color.” The Twitter hive-mind, as you can see, was sending me down the same path…

A typical example of a humic acid.

Next stop, humic acids. Now we’re getting somewhere. These are big molecules with several functional groups. The chemists out there will observe that, yes, they contain several carboxylic acid groups (the COOH / HOOC ones you can see in the example) so, yes, it makes sense they’d behave as acids.

“No nasties”, blk said. “Pure” they said. When you hear those sorts of things, do you imagine something like this is in your drink? Especially one that, let’s be clear, is a component of soil?

Oh, hang on, I should’ve checked the “blk explained” page on the blk water website. There’s a heading which actually says “what are Fulvic Minerals”, let’s see now…

“Fulvic minerals are plant matter derived from millions of years ago that have combined with fulvic acid forming rare fulvic mineral deposits. They deliver some of the most powerful electrolytes in the world.”

“Fulvic minerals contain 77 other trace minerals, most of which have an influence on the healthiness of our body. They are very high in alkaline and when sourced from the ground contain a pH of 9.”

I don’t know about you, but I’m not totally convinced. I mean, as @geolizzy says in her tweet here (excuse the minor typo, she means humic, not humid), it sounds a bit like… water contaminated with hydrocarbon deposits?

Yummy.

And, by the way, the phrase “very high in alkaline” is utterly meaningless. Substances are alkaline, or they containsubstances which are alkaline. “Alkaline” is not a thing in itself. This is like saying my tea is high in hot when sourced from the teapot.

There’s one more thing to add. So far this might sound a bit weird but… probably safe, right? What could be more wholesome than a bit of soil? Didn’t your granny tell you to eat a pinch of soil to boost your immune system, or something? At worst it’s harmless, right?

Tap water is chlorine-treated to keep it free of nasty bacteria.

Maybe. But then again… water is often treated with chlorine compounds to keep it bacteria-free. Now, blk water is supposedly spring water, which isn’t usually treated. But hypothetically, let’s consider what happens when humic acids, or fulvic acids, or whatever we’re calling them, come into contact with chlorine-treated water.

To sum up: it is black, and that’s kind of weird and a fun talking point – although if you like the idea of a black drink you can always drink cola. It doesn’t balance your pH levels – nothing does. I don’t believe it replenishes electrolyte levels either – how can it when it doesn’t contain sodium? – and I’m dubious about the “2 ingredients” claim (could you tell?). And the oh-so-healthy-sounding fulvic minerals are most likely due to contamination from coal deposits.

All in all, whilst it might not be quite such a conversation piece, I think it would be better to get Great-uncle Nigel a nice box of chocolates this year.

I believe that anyone that wants them should have easy access to the facts on this subject, and not just the information provided by proponents of MMS/CD use.

With this in mind I’ve written this post as a summary of the basics. I ask only that you credit me if you use this to write an article. A mention of my Twitter account, @chronicleflask, or a link to this page will suffice.

What is MMS?

MMS is usually sold as water purification drops

MMS stands for ‘master mineral solution’ or sometimes ‘miracle mineral solution’. It is a 22.4% solution of sodium chlorite in water. Sodium chlorite has the chemical formula NaClO2. So, MMS is 22.4 grams of NaClO2 dissolved in 100 mls of water. Sodium chlorite/MMS does not, on its own, act as a bleach.

Sodium chlorite’s LD50 (for rats) is 350 mg/kg. This means that, on average, if you feed rats 350 mg of it per kg of body weight, half the rats will die. If we assume its toxicity is similar in humans (and there’s no reason it should not be) that means that 5.25 grams would probably be enough to kill an average 4-year-old child weighing about 15 kg.

MMS is usually sold as ‘water purification drops’. Search for ‘sodium chlorite water purification’ in Google and you will quickly find it (usually alongside an ‘activator’ solution). Bottles for sale are usually 4 oz, or 114 mls. One quarter of one of these bottles would probably be lethal to a 15 kg 4-year-old.

What’s the connection between MMS and CDS?

The chemistry of sodium chlorite (the substance in MMS) with acids.

Chlorine dioxide evaporates quickly from solution, which means CD solutions cannot be stored – they have be made freshly as they’re needed. When sodium chlorite is mixed with an acid, usually citric acid (the acid in oranges and lemons), it forms chlorine dioxide. In short:

If sodium chlorite is mixed with citric acid is used the reaction doesn’t happen in one step. Rather, chlorous acid (HClO2) forms, which ultimately breaks down to form ClO2. Several reactions are involved in this process. The concentration of chlorine dioxide in a solution made in this way is likely to be lower than if hydrochloric acid is used. However, it’s important to realise the the resulting solution is a mixture of harmful substances. Less chlorine dioxide does not necessarily mean safer.

How much chlorine dioxide forms when MMS is ‘activated’?

It’s not possible to answer this precisely, because it depends on several different factors. To begin with, it depends on whether hydrochloric acid or another acid (such as citric acid) is used. It further depends on temperature, and how much acid is added. We have no way of knowing exactly what someone mixing up these solutions at home is doing.

A document on acidified sodium chlorite published by the Joint Expert Committee on Food Additives (JECFA) suggests that, at a pH of 2.3, a 50 ppm solution of sodium chlorite would produce 16 ppm chlorous acid (less at higher pHs). Starting with a 22.4% solution (as in MMS), and allowing for the stoichiometry suggested by the equations above, this could produce something in the region of 36 g of chlorine dioxide per litre of water.

The US EPA’s recommended safe limit for chlorine dioxide is 0.0008 grams per litre of water. Compare this to 36 grams per litre. Even if only a fraction is converted to chlorine dioxide, the resulting mixture is likely to be tens of thousands in excess of safe limits.

How are CD solutions used in food & drink production?

Very dilute solutions, with just a few ppm of chlorine dioxide, are used as sprays or dipping solutions for poultry, meats, vegetables fruit and seafood. However, in these applications the chlorine dioxide evaporates from the food long before anyone eats it – it’s not present in the final food product. Chlorine dioxide is also used in water treatment plants, but the concentration in the final water supply is strictly controlled so that it’s less than the recommended safe limits.

Humble and Rivera advocate drinking CD solutions and/or using them in enemas. Protocols for such treatments involve adding drops of CDS to water, milk or other liquids.

The number of drops used varies. Humble reportedly used 18 drops at a time in his malaria treatment. Usually this is added to further liquid, for example in a 250 ml bottle. Assuming a drop is 0.1 mls, this could be as much as 0.065 g of chlorine dioxide in 250 mls, or 0.26 grams per litre. Once again, US EPA’s recommended safe limit for chlorine dioxide is 0.00008 grams per litre.

The amounts recommended by MMS/CD protocols are likely to be at least 3000 times safe limits, and may be considerably more. Protocols exist which recommend drinking these mixtures every one or two hours, eight times a day or even more.

What would happen if someone drank a CD solution?

Chlorine dioxide exposure may actually cause delays in the development of the brain.

It would depend on the concentration. The very low levels used in normal water purification are not be harmful (that’s why safe limits exist), however drinking large amounts (such as those usually recommended in MMS/CD protocols) would cause irritation to the mouth, oesophagus, and stomach. There is no evidence that chlorine dioxide causes cancer. The ATSDR‘s (Agency for Toxic Substances and Disease Registry) entry for chlorine dioxide says that “studies in rats have shown that exposure of pregnant animals to chlorine dioxide or exposure of pups shortly after birth can cause delays in the development of the brain” (see also PMID: 2213920).

Children have thinner tissues than adults. The risks of regular enemas, particularly with a corrosive agent such as chlorine dioxide, and particularly when carried out at home by someone with no medical training, are likely to be considerably higher for children.

Is there any way to tell if someone has been using CDS in high concentrations?

Unless someone admits to using CDS, there isn’t really any way to tell. For this reason there are very few reported cases of harm caused by CDS, as users tend to be extremely secretive. Unless an enema causes major trauma (which is a real risk) the symptoms are likely to be fairly vague gastrointestinal distress, which could be caused by any number of other things. There is no routine medical test to measure chlorine dioxide or chlorite in the body. There is a special test to measure chlorite in tissues, blood, urine, and feces, but the test cannot tell the extent of the exposure or whether harmful effects will occur. This test wouldn’t be performed unless exposure was expected. In other words, unless someone admits to using CDS on themselves or their child, it’s unlikely anyone will ever find out.

If there’s no cure for autism/cancer/some other condition, mightn’t it be worth trying…?

Medicine is all about risks vs. benefits. The benefit of using a particular treatment must always exceed the risk of using that treatment. In this case, there are no proven benefits of using MMS/CDS. There are considerable risks, as described above. The only thing MMS/CDS will do is make you feel sick and generally more unwell than you (or your child) might already. So no, it isn’t worth trying. Please don’t.

Comments will be left open on this page for as long as it takes for me to tire of dealing with “you’re a pharma shill!”, “this is all lies!”, “watch this YouTube video that proves it works!” and “I drink it every day and I’m fine!” type comments. Annnnd that’s it. The most recent “you’re clearly paid off by corporations” comment has been deleted. Comments have been closed. Don’t go and comment on other pages: your comment will not be approved.

So what on earth was happening? An early suggestion was that copper salts were contaminating the water. It’s not unheard of for copper compounds to get into water supplies, and it would certainly explain the colour; copper chloride solutions in particular are famously greeny-blue. But what about that sulfurous smell? Copper chloride doesn’t smell of sulfur.

Was the strange pool colour due to an algae bloom, like this one in Lake Erie?

The most likely culprit was some sort of algae bloom – in other words rapid algae growth – with the smell probably coming from dimethyl sulfide, or DMS. There’s a singled-celled phytoplankton called Emiliania huxleyi which is particularly famous for producing this smelly compound. In fact, it actually has more than one very important role in nature: the smell is thought to alert marine life that there’s food nearby, but it also seeps into the atmosphere and helps with cloud formation, helping to control our planet’s temperature. Without these reactions, Earth might not be nearly so habitable.

But how did algae manage to grow in the pool? The pool chemicals should have prevented it, so what had happened? An Olympic official then went on to make the comment that “chemistry is not an exact science,” which of course led to much hilarity all around. Chemistry is, after all, incredibly exact. What chemistry student doesn’t remember all those calculations, with answers to three significant figures? The endless balancing of equations? The careful addition of one solution to another, drop by drop? How much more ‘exact’ would you like it to be?

But I had a bit of sympathy with the official, because I suspect that what they actually meant – if not said – was that swimming pool chemistry is not an exact science. And while that, too, is hardly accurate, it is true that swimming pool chemistry is very complicated and things can easily go wrong, particularly when you’re trying to work on an extremely tight schedule. They could hardly, after all, close down all the pools and spend several days carrying out extensive testing in the middle of the sixteen-day-long Olympic Games.

Rio 2016 Olympics Aquatics Stadium (Image: Myrtha Pools)

When a pool is first built and filled, things are, theoretically, simple. You know exactly how many cubic litres of water there are, and you know exactly how much of each chemical needs to be added to keep the water free of bacteria and other nasties. Those chemicals are added, possibly (particularly in a pool this size) via some kind of automated system, and the pH is carefully monitored to ensure the water is neither too alkaline (basic) nor too acidic.

Originally, water was treated to make it alkaline and then chlorine gas itself was added. This produced compounds which killed bacteria, in particular sodium hypochlorite, but the practice was risky. Chlorine gas is extremely nasty stuff – it has, after all, been used as a chemical weapon – and storing it, not to mention actually using it, was a dangerous business.

However, hundreds of people swimming in untreated water is a recipe for catching all kinds of water-borne disease, so it wasn’t long before alternatives were developed.

Those alternatives made use of the chemistry that was happening anyway in the water, but allowed the dangerous bit, with the elemental chlorine, to happen somewhere else. And so hypochlorite salts began to be manufactured to be used in swimming pools.

As the lovely graphic from Compound Interest illustrates, sodium hypochlorite reacts with water to form hypochlorous acid, which in turn goes on to form hypochlorite ions. These two substances sit in an equilibrium, and both are oxidants, which is good because oxidants are good at blasting bacteria. The equilibria in question are affected by pH though, which is one reason why, quite apart from the potential effects on swimmers, it’s so important to manage the pH of pool water.

There are a couple of different chemicals which can be added to adjust pH. Sodium bicarbonate, for example, can be used to nudge the pH up if needed. On the other hand, sodium bisulfate can be used to lower pH if the water becomes too alkaline.

UV light breaks down the chemicals that are used to keep swimming pool water clean.

This can all be managed extremely precisely in an unused, enclosed pool. But once you open that pool up, things become less simple. Open-air pools have a particular problem with UV light. Chlorine compounds are often sensitive to UV – this is why CFCs are such a problem for the ozone layer – and hypochlorite is no exception. In the presence of UV it breaks down in a process called photolysis to form chloride ions and oxygen. This means that outdoor pools require more frequent treatments, or the addition of extra chemicals to stabilise the ‘free available chlorine’ (FAC) levels.

Sadly, I haven’t managed to make it over to Rio, but from what I’ve seen the Aquatic Centre has a roof which opens up, which means that the pool water is indeed being exposed to UV light.

So perhaps the chemical levels simply dropped too low, which allowed algae to proliferate? Possibly aggravated by environmental conditions? Indeed, initially this seemed to be the explanation. FINA, the international governing body of aquatics, issued a statement on Wednesday afternoon which said:

“FINA can confirm that the reason for the unusual water color observed during the Rio diving competitions is that the water tanks ran out of some of the chemicals used in the water treatment process. As a result, the pH level of the water was outside the usual range, causing the discoloration. The FINA Sport Medicine Committee conducted tests on the water quality and concluded that there was no risk to the health and safety of the athletes, and no reason for the competition to be affected.”

This prompted people to wonder how on earth chemical levels were allowed to run out in an event as significant as the Olympics – did someone forget to click send on the order? – but still, it seemed to explain what had happened.

FINA issued a new statement on Sunday

Until today (Sunday), when more information surfaced as Olympic officials announced that they were going to drain at least one of the swimming pools and refill it. This is no small feat and will involve considerable cost: after all, we’re talking about millions of gallons of water. But it seems to be necessary. As Rio 2016’s director of venue management Gustavo Nascimento said:

“On the day of the Opening Ceremonies of the Games, 80 litres of hydrogen peroxide was put in the water. This creates a reaction to the chlorine which neutralises the ability of the chlorine to kill organics. This is not a problem for the health of anyone.”

Whoops. Yes indeed. Hydrogen peroxide reacts with chlorine to produce oxygen and hydrochloric acid. In fact, hydrogen peroxide is actually used to dechlorinate water which contains levels of chlorine that are too high. It might not be the very worst thing you could add to the water (when you think of all the things that could end up swimming pools) but it’s definitely up there.

Why and how this happened doesn’t, at the moment, appear to be clear. Presumably someone is for the high jump, and not just on the athletics field.

I happened to see an advert for Arm & Hammer toothpaste on TV a couple of days ago, in which they cheerfully proclaimed that it contained “liquid calcium”.

Calcium, on the left. With the metals.

This brought me up short. First thing: calcium is a metal. Now, as a famous British movie star might say (or perhaps might not say), “not many people know that”. Ask a roomful of people if calcium is a metal and most of them will tell you it’s not. I’ve even heard students who know what the periodic table is and what the position of elements within it means, and who can see calcium right there on the left hand side, express their doubts. Everyone associates calcium with bones and teeth, possibly rocks at a push. No one (other than chemists of course) hears ‘calcium’ and thinks of a silvery-grey metal.

But that is indeed what it is. It is a metal, and although its melting point isn’t huge in the grand scheme of metals, it’s still a fairly substantial 842 oC. The temperature in your bathroom is probably in the region of 20 oC. In fact your kitchen oven probably only goes up to about 240 oC, so the melting point of calcium is some 600 oC hotter than the hottest setting on your oven.

Calcium and water: what you can’t see is how hot this sucker is going to get.

Temperature problems aside, pure calcium is also highly reactive. Drop some in water and you’ll see a lot of violent bubbling followed by the solution turning white as a corrosive calcium hydroxide solution forms. The bubbling is due to flammable, potentially explosive, hydrogen gas. Oh, and it will get really, really hot too – this is what chemists call an exothermic reaction. I for one will confess to once (many, many years ago, of course) dropping a red-hot boiling tube into which I’d popped just a little too much calcium metal. After it had also bubbled up and covered my hand with the aforementioned calcium hydroxide. Ooopsie. (Fear not, my hand survived unscathed, after the application of copious amounts of cold water – the go-to cure for most chemical exposures).

So, at the risk of stating the obvious, there’s no liquid calcium in Arm & Hammer toothpaste. And a jolly good thing too.

What is there? At this point I should probably point out that Arm & Hammer are quite careful, in their literature and on their packaging, to always put a little ™ by “Liquid Calcium”. A quick glance at their website clarifies that they’re talking something called “Liquid Calcium ™ Technology” which refers to an ingredient that contains “up to 8 times more calcium and phosphate ions than the amount found in saliva so it is able to replenish ion content in your mouth and subsequently re-mineralise and protect your teeth more efficiently.”

Ah, now we get to the truth of the matter. It’s not liquid calcium, but calcium ions in solution.

Does this matter? Am I being unnecessarily pedantic? Liquid/solution, calcium metal/calcium ions, what’s the difference?

When an extra O really matters.

Well, the thing is, chemists are pedantic. See, in chemistry, it genuinely could be a matter of life and death. Ethanol, for example, is ‘drinking’ alcohol. It’s the stuff in beer, and wine, and strawberry daiquiris. It may not be exactly healthy, but most adults can consume some fairly safely. Ethanal, on the other hand, is a toxic and probably carcinogenic substance that’s mainly used industrially as a starting point to make other chemicals.

To pick another example, chlorine is a highly toxic gas that’s been used in chemical warfare; chloride ions are found in salt and are consumed perfectly safely every day. The difference between ions (atoms or molecules which have become charged due to the gain, or loss, of electrons) and atoms is really quite critical in chemistry, and in life in general.

Potassium reacting with water – pretty!

‘Everybody’ knows that bananas contain lots of potassium. But potassium is another highly-reactive metal. In fact it’s even more reactive than calcium. Potassium explodes with a rather beautiful lilac flame in contact with water. It’s pretty to watch, but you wouldn’t want it in your mouth. Actually bananas contain potassium ions (and just to really mess with everything you thought you knew, not even that much compared to lots of other foods).

Back to the dubious labelling again, It’s interesting that Arm & Hammer have chosen to say “fluoride” – which specifically, and correctly, refers to fluoride ions – and not “liquid fluorine”. I mean surely, in the spirit of consistency, it should be liquid fluorine and liquid calcium (argh!), or fluoride ions and calcium ions.

The word liquid has a specific meaning in chemistry. It means a pure element or compound in its molten state. Pure water at room temperature is a liquid. So is ethanol, and mercury, and bromine (interestingly these last two are the only chemical elements which are liquids at room temperature). Ethanol dissolved in water, as it is in strawberry daiquiris (more or less), isn’t a liquid. It’s a solution. This matters. Liquid ethanol is pure ethanol. Drink that and you’re looking serious alcohol poisoning in the face, and it’s about to wallop you for looking at it funny.

An Arm & Hammer chemist?

Saying, or even implying, that calcium ions in solution is ‘liquid calcium’ is like saying that seawater is liquid sodium (sodium is another highly reactive metal – orange flame this time). It’s just nonsense. Ok, it’s probably not going to cause anyone any actual harm, but that’s not the point. It’s completely factually inaccurate. I am absolutely certain that the chemists working for Arm & Hammer wanted to tear their hair out when the advertising company came up with this name for the formulation they’d spent (probably) years slaving over. And I expect they were essentially told to shut up about it, the vast majority of our customers won’t know the difference.

And sadly this may be true. But it shouldn’t be. Would Arm & Hammer care if their boxes were labelled ‘tothpast’ instead of toothpaste? I bet they’d be bothered if the boxes were priced at £250 instead of £2.50. Why fuss over spelling and numbers but be careless over scientific literacy? Either precision matters or it doesn’t.

Perhaps it’s time scientists starting making as much noise about this kind of thing as people who complain about stray apostrophes or the misuse of the word disinterest. You never know, it might help levels of scientific understanding.

Mind you, perhaps the author of a blog called The Chronicle Flask shouldn’t throw stones…

—-

After I wrote this post I tweeted something referring to “liquid phosphorous”. It was pointed out to me, quite rightly, that I meant “liquid phosphorus”. Phosphorus is the noun – the name of the chemical element – and phosphorous is an adjective. As in, “phosphorous fertiliser”. I confess I was a bit hazy on that one until made to check, which is ironic really. Consider me sent to the back of the class 😉